Storage battery



STORAGE BATTERY original Filed Mayen 9, 1955 Arroz/v5 Ys jPavtentecl' Feb. `11, `1936 v l l g` "f H v l'zosoau 1 Y Y l #STQRAGaBATrER rifwiuara L. Reinhardt-shakerHeights; ohio, as: i signOrtoWiIIard :Storagei'Battery Company,`

y, i Cleveland', Ohio, acorporationlof. West Virginia ,ofiginalzaplition March 9, 1933, ser'arno. 111660,116. Divided and this application Septem` berfvao, 1933,l"scrittlito. 690,217,i` H .f `7ClaixsfiClQlsoQac) n p This inventionfrelates tofstorage batteries of i One of Athe'ob'jects of thepresent' invention is the`leat1--acid`type, andjspeoially'to the method Ato provide a suitablescombinationf'ofexpanders `oi? `makingfthe platesjof such'batteries, particuin the paste or active 'material'- and the desired "larly the"negativelp'l'ates.v This application is a proportionof the expanders." f

5 continuationL inl part of my` application Serial The single gu "e of thedrawing is a conven.-` 5` No. 291,139, filedfJuly 7, 1928, and a divisionof -tional representation of a battery plate. my application Serial No. A660,116, led March 91,1 In carrying out the invention,` for one of*` the 1933. expanders'I prefer to employ humic acid because O rdinarily,the` negative plateis made by ap-j of thel fact thatl it increases` the life and capacity l0 plying to a framework o-r grid of antimony lead 0f the negativeplate, as explained above. Hurnic 10 a paste containing'one' or more lead oxides which `acid may be accompanied by one or more other I later in the forming orcharging operation are `V`substances the number `and nature of which deconverted electrolytically-into spong'ylead.Y This "pend on the source orI the manner inwhich the-- spongylead is metallic leadin very finely divided humic acid is produced. Forexample, it is poscondition and forms the active material of the sible-to employ 'either artificial orunatural humic 15 negative plate. y 'i H Y "substances, 'An example of an articial sub- Itis commonpracticeto-combine'with the lead f stance is humic acid rmade bythe action of suloxide orV oxides usedf informing the pastef for phuricfacid on certain carbohydrates. It can the negative plate an inert material `which per `be `produced in other Ways with one or all of y, forms the function of separating the small pari Whchthe humic acid may have associated with 20 ticles of nelydivided metallic lead, thus preit somewhat analogous acids, 'such as' ulmlc, venting them from adhering together and form- Y aprccrinic and crenic acids, which may in theming larger particles-"If this inert material, which *selves have a benecial eiect in the active ma-L is commonly called expander, is not present, terial, Vbut with the humicA acid predominating relatively'large particles of metallic leadwil1-"be"- 4.or constituting the chief ingredient'. Examples 25 formed and the active surface of the active maj of natural humic substances are peat and brown terial will be reduced, i and this will lessenthe coal each of which I believe is composed chiefly" capacityand reduce the'elective life of thev neg- Y lof humic acid. Therefore, in View of the fact ative plate. f d i "that humic'acid maybe accompanied by other Manyinert materials have been used'for ex" materials, When the term humic substance is 30 panders informingthe `paste for negative"` plates, y used, I mean'humic acid alone or humic acid assuch, forexample, as barytes, bla-ncifixe, silica, sociated with one or Vmore other substances with carbony black, lampbla'ck, graphite,'eto. These the humic acid preferably D1@flIIlrlilSiIlg materials employed as expanders arepractically For the otherl expander which is to be used insolublein sulphuric acid used in making the` with the humic substance, several may be em- 35 paste and inthesulphuric l-acid of the electrolyte"Y ployed. I prefer to use barium sulphate although of the finished battery. f lsulphates of other alkaline earth metals, such as Ir"1`U.'S. Patentfflo. "1,817,846, issued in my calciu1n`or strontium, may be employed, and name',`th`ere` is described land claimed an impor' doubtless still others are available, but a sul-l 40` tant improvement in expanders` which` consists phateof one of the alkaline earth metals, such 4l) in the discovery of al new1 expander composed- `as barium, is employed not only because it'serves chiefly of or ccntainingjhumic acid. Humc acid, Well in the lead `materialas an expanden-but bein addition to having the properties `of, other l cause it can be applied along with the humic sub- .expanders as describedabove, `also has certain stance by the precipitation process, as will next other distinct advantages one of whichis that be explained. x

it increases the capacity and life of the `negative` Whileit is not essentalto this invention that pole plate, This additional; capacity produced' the expanders be` applied in the manner next to by humic acid is more pronounced when the bat` be explained, I have discovered that, if the two tery is discharged at `temperatures below normal `expanders can be precipitated in the lead com- ;,0 than at normal orzhigher temperatures, While" pound, Vand particularly if they can be simultagood resultsare obtainedjby vthe use-ofhuinic" neously precipitated from a single solution, they acid in the manner relatedin'the above patent, would be uniformly distributed and would be in Irid that the best resultsv are obtained by using very fine condition, as isl desirable toobtain the with the humic-acid another expander suchas bestV results?l I'made the discovery that this is "f one of" those previously used.` possible, and that they can both be precipitated 55 from a single solution, as will now be explained. I might say at this point that it is immaterial whether the expanders which are iny solution and which are to be precipitated in the lead compound are chemically combined, as for example as a humate of one of the alkaline earth metals, or whether they are in solution uncombined, as will be explained below. It is obvious, therefore, that I may proceed in different ways and with diierent materials, but very good results have been obtained by proceeding as follows:

By treating the humic substance with a suitable solution of an alkaline earth metal, I obtain a solution containing the metal which I believe to be combined with the humic acid as a humate. For example, I may treat the humic substance with a solution of barium hydroxide and obtain what I believe to be barium humate. This barium humate solution is then incorporated in the paste or active material in any one of several Ways hereinafter described, and then by treating the lead material, to which the humate has been applied with a suitable reagent, such as sulphuric acid, the two expanders, barium sulphate and humic acid, are simultaneously precipitated, both these substances being insoluble in sulphuric acid. It will be understood, of course, that instead of forming and utilizing for this purpose barium humate, I may form and utilize a humate of other alkaline earth metals, such as those mentioned above.

As stated above, I do not regard it necessary that the solution consist of a humate or of a solution wherein the metal and the humic acid are chemically combined. For example, the articial or natural humic substance may be dissolved in an alkaline solution and one of the alkaline earth metals, such as barium, calcium, or strontium, may be added to the same solution as a hydroxide. Whether the dissolved humic substance and the hydroxide of the alkaline earth metal remain as such in solution or whether they combine to form a humate is immaterial to the invention. The remainder of the process is the same whether the solution is obtained in lany of the ways above stated, i. e., whether the materials are combined or uncombined.

As before stated, when the solution from which the two expanders are to be precipitatedy is prepared, I may proceed in different ways. I may form the paste by mixing with the leadoxide or oxides the solution from which the expanders are to be later precipitated, and after the solution has been thoroughly mixed with the oxide or oxides, the expanders may be precipitated in the paste by adding and thoroughly mixing with the paste a mineral acid, such as sulphuric acid. vA part of the sulphuric acid will react with the solution which, for convenience, will be assumed to be barium humate, forming barium sulphate and humic acid, both of which are precipitated in very lnely divided form uniformly throughout the paste. Likewise, if the materials are not combined, the sulphuric acid will react with the hydroxide of the alkaline earth metal forming a sulphate of the metal, and will at the same time precipitate humic acid since the latter is insoluble in sulphuric acid. In the latter case, as in the former, the two expanders are precipitated in nely divided condition and uniformly through out the paste.

It is unnecessary that the sulphuric acid or other reagent which causes precipitation be added to the paste formed by mixing the lead oxide or oxides with the solution from which the ex- 2,oso,7 17

panders are to be precipitated, but the solution alone may be used with the oxide or oxides to make the paste, and after the mix has been made and the plates have been pasted, the plates may be dipped into a solution of a precipitating reagent, such as sulphuric acid, long enough for the reagent to permeate the paste and cause the lprecipitation of the two expanders, or the plates thus pasted may be dried without dipping and may then be formed or charged in the usual manner in an electrolyte of sulphuric acid which converts the paste of the negative pole plates into active material or spongy lead. In this operation, the Asame results are obtained as before. Or the paste may be made without using the solution and later either the pasted plates or the formed or charged plates may be dipped into the solution until it thoroughly permeates the Same, and then into sulphuric acid to cause the precipitation of the two expanders, as before. However, I prefer to cause the precipitation of the two expanders by bringing together in the paste before it is applied to the grids the solution and the sulphuric acid, so as to bring about the precipitation of the two expanders uniformly in the paste rather than by causing the precipitation in either the pasted or the formed plates,

It is of course possible to vary the amount of humic acid or substance and the other expander which are thus introduced into the paste or active material by varying the concentration of the humate in solution which is incorporated in the paste or active material or the concentration of the solutions which are mixed as explained above. It is possible also to vary the ratio of the two expanders for, in making up the solution, it is possible to employ an excess of one or the other of the compounds used in making the solution.

I prefer that the amount of each of the expanders incorporated in the paste or active material in the manner above explained vary from about 0.1% to about 1% by weight. In the case of the humic substance, I prefer that the humic acid content thereof be within the range stated. I might say that while about equal amounts of the two expanders may in some instances be employed, generally such will not be the case. I

may maintain the amount of one expander constant and vary the amount of the other. For example, the amount of humic acid that is employed will generally depend upon the conditions under which the battery is used. Usually the plates of batteries which are discharged at lower temperatures are provided with a greater percentage of humic acid.

It is obvious that instead of precipitating the expanders in the paste or active material, they may be added to 'the oxide or oxides whenv the paste is being made up, i. e., at the time the expander is usually added.

I'might add that the expanders are inert, i. e., they have no deleterious effect on the battery, and, as they are practically insoluble in sulphuric acid, they will remain in the plates and function therein throughout the life of the battery.

Above I have described my invention as applied to the production of negative plates. It may also be used in the production of positive plates, that is to say, it may be used in the production of both the positive and the negative plates, but I now believe it will be suflcient if the expanders are incorporated in the negative plates.

In the drawing I have shown conventionally a typical storage battery plate composed of .a grid I0, formed of lead or antimony lead, and the paste l oractive materialll `which contains two ex-1 br active material in any of the ways above mentioned. 1

panders which mayv be incorporatedl in the paste By the `conjoint use of two lexpanders in the active material, `such as a humic substance and one of the other expanders such as commonly emi ployedlor one ot those previously mentioned herein,v results are obtained which are not obtainable by the use of either expander alone.` For ex-v thefcapaclty and the life of the negative pole plates are increased, particularly for low temperaturewservicebut the increased capacity does not extend over the desired number ofcycles of operation.` On the other hand, if one o! the ordinary expanders is used alone,` the negative pole plates n donot have the desiredwcapacity particularly for low temperature service.

i fore."A

Having thus described my invention, I claimt l. A lead compound for plates of storage batteries of the lead-acidi type having distributed therethrough `a `humic :substance and a `sulphate oan alkaline earth metal. y t y 2. Al lead compound for plates of storage bat-j teries of the lead-acid type having two expander-s f distributed therethrough one consisting oiY'a` humic substance inl anvamount from substantially y d However, `when the humicfsubstance and one of the'other expanders i 0.1% to `substantially 1% by weight and the other consisting oi" a sulphate of an alkaline earth metal.

3. A lead compound for plates of storage bat-A teries of the lead-,acid type having two expanders substantially uniformly l distributed Ythroughout the same, one consisting of ahumic substance and the other a sulphate of an alkaline earth. metal in an amount from substantially 0.1% to substantially 1% by weight. ample,` if the humic substance is used alone, both teries ofy the lead-acidl type havingv distributed 41A lead compound for plates of storage battherethrough a humic substance and a sulphate of an alkaline earth metal each in an'amount from substantially 0.1% tosubstantially 1% by weight.

5. A lead compound forplates of storage bathumic acid and the other consisting of a sulphate of an alkaline earth metal.

Y "6; A lead compound for plates of storage batteries of the lead-acid typehaving distributed i therethrough in ilnely divided form a humic substance and the sulphate of `an alkaline earth metal. i

teries ofthe lead-acid type having uniformly distributed therethrough two expanders one consist-` ing of a humicsubstance composed chietlylof 20l 7. A lead `compoundfor plates of storage batteries of the lead-acid type having distributed therethrough in ilnely divided form a humic substance composed chiefiy of humic acid in. an

famount from substantially 0.1 to substantially 

